CN112088179A - 热塑性聚氨酯树脂制造用双液固化型组合物、热塑性聚氨酯树脂以及纤维强化树脂 - Google Patents
热塑性聚氨酯树脂制造用双液固化型组合物、热塑性聚氨酯树脂以及纤维强化树脂 Download PDFInfo
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- CN112088179A CN112088179A CN201980028487.5A CN201980028487A CN112088179A CN 112088179 A CN112088179 A CN 112088179A CN 201980028487 A CN201980028487 A CN 201980028487A CN 112088179 A CN112088179 A CN 112088179A
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- diol
- polyurethane resin
- thermoplastic polyurethane
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/08—Polyurethanes from polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/24—Catalysts containing metal compounds of tin
- C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
- C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3215—Polyhydroxy compounds containing aromatic groups or benzoquinone groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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Abstract
提供一种混合粘度低且固化后的玻璃化转变温度高的热塑性聚氨酯树脂制造用双液固化型组合物、作为其固化物的热塑性聚氨酯树脂以及包含该热塑性聚氨酯树脂的纤维强化树脂。热塑性聚氨酯树脂制造用双液固化型组合物具有包含二醇(A)的多元醇组分以及包含二异氰酸酯(B)的多异氰酸酯组分,所述二醇(A)包含分子量为200~700的具有芳香环的二醇(A‑1)和分子量为500以下的不具有芳香环的二醇(A‑2),所述二醇(A‑1)相对于所述二醇(A‑1)与所述二醇(A‑2)的合计的质量比((A‑1)/((A‑1)+(A‑2)))为(10/100)~(75/100)。
Description
技术领域
本发明涉及热塑性聚氨酯树脂制造用双液固化型组合物、热塑性聚氨酯树脂以及纤维强化树脂。
背景技术
纤维强化树脂由于其重量轻且具有优异性能,因此被广泛用于电气/电子部件、车辆以及飞机等领域。纤维强化树脂大多使用环氧树脂等热固性树脂作为基质。
另一方面,由于能够在树脂固化后再成形,因此开发了使用热塑性的聚氨酯树脂作为基质树脂的纤维强化树脂。在公开了热塑性的聚氨酯树脂的专利文献1中,使用聚碳酸酯二醇作为二醇。另外,在专利文献2中,使用聚醚碳酸酯二醇作为二醇。
现有技术文献
专利文献
专利文献1:日本特开昭63-305127号公报
专利文献2:日本特开2005-232447号公报
发明内容
发明欲解决的技术问题
然而,由于专利文献1的聚碳酸酯二醇与多异氰酸酯的混合粘度高,因此存在树脂成形时的作业性等差这样的问题。另外,由于专利文献2的使用聚醚碳酸酯二醇而生成的聚氨酯树脂的玻璃化转变温度低,因此存在纤维强化树脂的使用环境受到限制这样的问题。
本发明是为了解决上述问题而完成的,其目的在于提供一种混合粘度低且固化后的玻璃化转变温度高的热塑性聚氨酯树脂制造用双液固化型组合物、作为其固化物的热塑性聚氨酯树脂以及包含该热塑性聚氨酯树脂的纤维强化树脂。
用于解决问题的技术手段
(1)为了解决上述问题,本发明的热塑性聚氨酯树脂制造用双液固化型组合物具有包含二醇(A)的多元醇组分以及包含二异氰酸酯(B)的多异氰酸酯组分,其中,所述二醇(A)包含分子量为200~700的具有芳香环的二醇(A-1)和分子量为500以下的不具有芳香环的二醇(A-2),所述二醇(A-1)相对于所述二醇(A-1)与所述二醇(A-2)的合计的质量比((A-1)/((A-1)+(A-2)))为(10/100)~(75/100)。
(7)另外,本发明的热塑性聚氨酯树脂包含所述热塑性聚氨酯树脂制造用双液固化型组合物的反应物。
(8)另外,本发明的纤维强化树脂包含所述热塑性聚氨酯树脂和强化纤维。
发明效果
根据本发明,能够提供即使混合粘度低也能够形成具有高玻璃化转变温度的热塑性聚氨酯树脂的热塑性聚氨酯树脂制造用双液固化型组合物、该热塑性聚氨酯树脂以及包含该热塑性聚氨酯树脂的纤维强化树脂。
具体实施方式
首先,列述并说明本发明的实施方式的内容。
(1)本发明的实施方式涉及的热塑性聚氨酯树脂制造用双液固化型组合物是具有包含二醇(A)的多元醇组分以及包含二异氰酸酯(B)的多异氰酸酯组分的双液固化型组合物,所述二醇(A)包含分子量为200~700的具有芳香环的二醇(A-1)和分子量为500以下的不具有芳香环的二醇(A-2),所述二醇(A-1)相对于所述二醇(A-1)与所述二醇(A-2)的合计的质量比((A-1)/((A-1)+(A-2)))为(10/100)~(75/100)。
根据这样的组成,即使多元醇组分与多异氰酸酯组分的混合粘度低,也能够形成具有高玻璃化转变温度的聚氨酯树脂。另外,由于混合粘度低,因此还能够提高例如树脂成形时的作业性。
(2)优选地,所述不具有芳香环的二醇(A-2)是脂肪族二醇和具有氧亚烷基的二醇中的至少任一者。
根据这样的组成,即使多元醇组分与多异氰酸酯组分的混合粘度低,也能够形成具有更高玻璃化转变温度的聚氨酯树脂。
(3)优选地,所述二异氰酸酯(B)包含芳香族二异氰酸酯(B-1)。
根据这样的组成,即使多元醇组分与多异氰酸酯组分的混合粘度低,也能够形成具有更高玻璃化转变温度的聚氨酯树脂。
(4)优选地,所述具有芳香环的二醇(A-1)是双酚A的环氧烷加成物。
根据这样的组成,即使多元醇组分与多异氰酸酯组分的混合粘度低,也能够形成具有更高玻璃化转变温度的聚氨酯树脂。
(5)优选地,所述多元醇组分还包含多孔质粉体(C)。
根据这样的组成,即使多元醇组分与多异氰酸酯组分的混合粘度低,也能够形成具有更高玻璃化转变温度的聚氨酯树脂。
(6)优选地,热塑性聚氨酯树脂制造用双液固化型组合物用于纤维强化树脂的制造。
通过使用这样的混合粘度低的热塑性聚氨酯树脂制造用双液固化型组合物的组成,能够将例如成形时的树脂粘度抑制得很低,因此,能够提高与强化纤维复合化时的基质树脂的流动性,并提高成形作业性,并且能够提高得到的纤维强化树脂制造的玻璃纤维温度。
(7)本发明的实施方式涉及的热塑性聚氨酯树脂包含热塑性聚氨酯树脂制造用双液固化型组合物的反应物。
如上所述,通过包含热塑性聚氨酯树脂制造用双液固化型组合物的多元醇组分和多异氰酸酯组分的反应物的构成,改善混合时及成形时的作业性,并且热塑性聚氨酯树脂具有高的玻璃化转变温度。
(8)本发明的实施方式涉及的纤维强化树脂包含所述热塑性聚氨酯树脂和强化纤维。
通过这样的组成,纤维强化树脂的制造时的作业性得以改善,并且纤维强化树脂具有高的玻璃化转变温度。
在本公开中,对于聚丙二醇等这样具有分子量分布的化合物,“分子量”表示数均分子量。
[热塑性聚氨酯树脂制造用双液固化型组合物]
本发明的实施方式涉及的热塑性聚氨酯树脂制造用双液固化型组合物至少由包含二醇(A)的多元醇组分以及包含二异氰酸酯(B)的多异氰酸酯组分组成。双液固化型组合物是指例如通过混合两种液体而固化的树脂的原料。
[多元醇组分]
本发明的实施方式涉及的热塑性聚氨酯树脂制造用双液固化型组合物中的多元醇组分包含二醇(A)。
[具有芳香环的二醇(A-1)]
本发明的实施方式涉及的二醇(A)包含分子量为200~700的具有芳香环的二醇(A-1)。作为具有芳香环的二醇(A-1),除了分子量为200~700以外没有特别限制。
例如,作为具有芳香环的二醇(A-1),可举出4,4'-二羟基二苯醚、双酚S、双酚A或4,4'-二羟基二苯砜。另外,作为具有芳香环的二醇(A-1),例如可举出苯二甲醇、对苯二酚、4,4'-双酚、4,4'-二羟基二苯醚、双酚S、双酚A或4,4'-二羟基二苯砜等环氧烷加成物。作为环氧烷,可举出环氧乙烷、环氧丙烷、环氧丁烷、α-烯烃氧化物等。具有芳香环的二醇(A-1)可以包含2种以上的这些化合物。
作为具有芳香环的二醇(A-1),从提高所得到的树脂的玻璃化转变温度的观点出发,优选在1分子中具有2个以上苯环的二醇,更优选双酚A的环氧烷加成物,进一步优选双酚A的环氧乙烷加成物或环氧丙烷加成物。
具有芳香环的二醇(A-1)的分子量如上所述为200~700,从提高得到的树脂的玻璃化转变温度的观点出发,更优选为300~600,进一步优选为350~500。
[不具有芳香环的二醇(A-2)]
本发明的实施方式涉及的二醇(A)除了包含分子量为200~700的具有芳香环的二醇(A-1)以外,还包含分子量为500以下不具有芳香环的二醇(A-2)。作为不具有芳香环的二醇(A-2),例如能够举出以下说明的脂肪族二醇、具有氧亚烷基的二醇以及脂环式二醇等。不具有芳香环的二醇(A-2)可以包含2种以上的这些化合物。
作为本发明的实施方式涉及的脂肪族二醇,没有特别限制,例如可举出:乙二醇、1,2-丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、新戊二醇、3-甲基-1,5-戊二醇、2-丁基-2-乙基-1,3-丙二醇、2-甲基-1,3-丙二醇、2-乙基-1,3-己二醇。本发明的实施方式涉及的脂肪族二醇可以包含2种以上的这些化合物。
作为本发明的实施方式涉及的脂肪族二醇,特别优选1,4-丁二醇、2-乙基-1,3-己二醇。
作为本发明的实施方式涉及的具有氧亚烷基的二醇,没有特别限制,可举出乙二醇、二乙二醇、丙二醇、二丙二醇、三丙二醇、1,3-丁二醇、1,4-丁二醇等二元醇与环氧乙烷、环氧丙烷、环氧丁烷和α-烯烃氧化物等环氧烷的加成聚合物。本发明的实施方式涉及的具有氧亚烷基的二醇可以包含2种以上的这些化合物。
作为本发明的实施方式涉及的具有氧亚烷基的二醇,优选为二元醇与环氧丙烷的聚合加成物,进一步优选二丙二醇、三丙二醇。
作为本发明的实施方式涉及的脂环式二醇,没有特别限制,能够举出1,4-环己二醇、1,4-环己烷二甲醇、加氢双酚A等。
本发明的实施方式涉及的不具有芳香环的二醇(A-2)的分子量如上所述为500以下,从抑制混合粘度并且提高得到的树脂的玻璃化转变温度的观点出发,优选为400以下,更优选为300以下,更优选为200以下,进一步优选为100以下。
在本发明的实施方式中,从抑制混合粘度并且提高得到的树脂的玻璃化转变温度的观点出发,具有芳香环的二醇(A-1)相对于100质量份二醇(A)优选为10~80质量份,更优选为20~70质量份,进一步优选为30~65质量份,进一步优选为40~60质量份。
在本发明的实施方式中,在多元醇组分所包含的多元醇中,从抑制混合粘度并且提高得到的树脂的玻璃化转变温度的观点出发,二醇(A)优选为80质量%以上,更优选为90质量%以上,进一步优选为95质量%以上,进一步优选为98质量%以上。在本发明的实施方式中,作为与多异氰酸酯组分反应的多元醇组分,为了形成热塑性树脂而使用了2官能团的多元醇、即多异氰酸酯,但是在可得到热塑性树脂的范围内,也可以包含3官能团以上的多元醇。
在本发明的实施方式中,多元醇组分中可以包含一元醇、多胺化合物等与二异氰酸酯(B)反应并固化的其他化合物。
在本发明的实施方式中,具有芳香环的二醇(A-1)相对于具有芳香环的二醇(A-1)与不具有芳香环的二醇(A-2)的合计的质量比((A-1)/((A-1)+(A-2)))为(10/100)~(75/100),从抑制混合粘度并且提高得到的树脂的玻璃化转变温度的观点出发,优选为(20/100)~(65/100),更优选为(30/100)~(60/100),进一步优选为(40/100)~(60/100)。
[多异氰酸酯组分]
本发明的实施方式涉及的热塑性聚氨酯树脂制造用双液固化型组合物中的异氰酸酯组分包含二异氰酸酯(B)。作为二异氰酸酯(B),没有特别限制,可举出脂肪族二异氰酸酯、脂环式二异氰酸酯、芳香族二异氰酸酯(B-1)和芳香脂肪族二异氰酸酯。本发明的实施方式涉及的二异氰酸酯(B)可以包含2种以上的这些化合物。
作为本发明的实施方式涉及的脂肪族二异氰酸酯,可举出:四亚甲基二异氰酸酯、十二亚甲基二异氰酸酯、六亚甲基二异氰酸酯、2,2,4-三甲基六亚甲基二异氰酸酯、2,4,4-三甲基六亚甲基二异氰酸酯、赖氨酸二异氰酸酯、2-甲基戊烷-1,5-二异氰酸酯、3-甲基戊烷-1,5-二异氰酸酯等。
作为本发明的实施方式涉及的脂环式二异氰酸酯,可举出:异佛尔酮二异氰酸酯、加氢二甲苯二异氰酸酯、4,4'-二环己基甲烷二异氰酸酯、1,4-环己烷二异氰酸酯、甲基亚环己基二异氰酸酯、1,3-双(异氰酸根合甲基)环己烷等。
作为本发明的实施方式涉及的芳香族二异氰酸酯(B-1),可举出:甲苯二异氰酸酯、二苯基甲烷二异氰酸酯(MDI)、4,4'-二苄基二异氰酸酯、1,5-萘基二异氰酸酯、二甲苯二异氰酸酯、1,3-苯二异氰酸酯、1,4-苯二异氰酸酯等。作为二苯基甲烷二异氰酸酯,可举出2,2'-二苯基甲烷二异氰酸酯、2,4'-二苯基甲烷二异氰酸酯、4,4'-二苯基甲烷二异氰酸酯。
作为本发明的实施方式涉及的芳香脂肪族二异氰酸酯,可举出二烷基二苯基甲烷二异氰酸酯、四烷基二苯基甲烷二异氰酸酯、α,α,α,α-四甲基苯二甲基二异氰酸酯等。
作为本发明的实施方式涉及的二异氰酸酯(B),可以是使含异氰酸酯基化合物与含羟基化合物反应而得到的异氰酸酯基末端聚氨酯聚合物改性体以及碳二亚胺改性体等改性体。
作为本发明的实施方式涉及的二异氰酸酯(B),从抑制混合粘度并提高得到的树脂的玻璃化转变温度的观点出发,优选芳香族二异氰酸酯(B-1),进一步优选二苯基甲烷二异氰酸酯、二苯基甲烷二异氰酸酯的碳二亚胺改性体。作为二苯基甲烷二异氰酸酯,优选2,4'-二苯基甲烷二异氰酸酯。
在本发明的实施方式中,在多异氰酸酯组分所包含的多异氰酸酯中,二异氰酸酯(B)优选为80质量%以上,更优选为90质量%以上,进一步优选为95质量%以上,进一步优选为98质量%以上。在本发明的实施方式中,作为与多元醇组分反应的异氰酸酯组分,为了形成热塑性树脂而使用2官能团的异氰酸酯即二异氰酸酯,但是在可得到热塑性树脂的范围内,可以包含3官能团以上的多异氰酸酯。
在本发明的实施方式中,在二异氰酸酯(B)中,芳香族二异氰酸酯优选为80质量%以上,更优选为90质量%以上,进一步优选为95质量%以上,进一步优选为98质量%以上。
[多孔质粉体(C)]
从提高树脂、具体而言是固化涂膜的拉伸物性的观点出发,本发明的实施方式涉及的多元醇组分可以包含多孔质粉体(C)。作为多孔质粉体(C),优选无机的多孔质粉体,更优选沸石。相对于100质量份的该多元醇组分,多孔质粉体(C)优选使用1~10质量份,更优选使用2~8质量份,进一步优选使用3~7质量份。
[双液固化型组合物]
本发明的实施方式涉及的热塑性聚氨酯树脂制造用双液固化型组合物(以下,简称为双液固化型组合物)包含上述多元醇组分和上述多异氰酸酯组分,通过这些多元醇组分和多异氰酸酯组分的反应而生成热塑性树脂。即,该双液固化型组合物具有反应生成物为热塑性树脂这样的性质。双液固化型组合物是双液固化性的树脂组合物,其将多元醇组分作为第1液,将多异氰酸酯组分作为第2液,并能够通过将这些第1液与第2液混合而使两组分反应固化。
本发明的实施方式涉及的双液固化型组合物中可以包含用于促进多元醇组分与多异氰酸酯组分的反应的催化剂。作为催化剂,能够使用通常在聚氨酯树脂的制造中使用的金属催化剂、胺类催化剂。作为金属催化剂,能够举出:二月桂酸二丁基锡、二月桂酸二辛基锡、二辛酸二丁基锡等的锡催化剂;辛酸铅、辛烯酸铅、环烷酸铅等的铅催化剂;以及辛酸铋、新癸酸铋等的铋催化剂等。作为胺类催化剂,可举出三乙二胺等叔胺化合物等。这些催化剂能够单独使用或组合使用。
在本发明的实施方式涉及的双液固化型组合物中,除此以外,还可以根据需要包含:增塑剂、阻燃剂、抗氧化剂、吸湿剂、防霉剂、硅烷偶联剂、消泡剂、表面调节剂、内部脱模剂等各种添加剂。
在本发明的实施方式涉及的双液固化型组合物中,异氰酸酯基与羟基等的活性氢基团的摩尔比(NCO/活性氢基团)没有特别限制,可以为0.5以上,可以为0.6以上,可以为0.8以上。另外,该摩尔比(NCO/活性氢基团)可以为1.5以下,可以为1.3以下,可以为1.2以下。
本发明的实施方式涉及的双液固化型组合物在25℃环境下的混合5分钟后的粘度没有特别限制。举出一例,粘度优选为700mPa·s以下,更优选为600mPa·s以下,进一步优选为500mPa·s以下,特别优选为300mPa·s以下。
需要说明的是,本发明的实施方式涉及的双液固化型组合物具有两液,即第1液和第2液,但只要是至少两液,也可以具有3液以上。
[热塑性聚氨酯树脂]
本发明的实施方式涉及的热塑性聚氨酯树脂是包含上述多元醇组分与上述异氰酸酯组分的反应物的热塑性树脂,作为一个实施方式,通过使上述双液固化型组合物反应而得到热塑性聚氨酯树脂。
本发明的实施方式涉及的聚氨酯树脂的玻璃化转变温度(Tg)没有特别限制。玻璃化转变温度例如优选为80℃以上,更优选为100℃以上,进一步优选为120℃以上。玻璃化转变温度的上限没有特别限制,例如为可以为200℃以上。
[纤维强化树脂]
本发明的实施方式涉及的纤维强化树脂包含作为上述的双液固化型组合物的固化物的热塑性聚氨酯树脂以及强化纤维。具体而言,该热塑性聚氨酯树脂被用作纤维强化树脂中的基质树脂。
作为强化纤维,没有特别限定,例如可举出:碳纤维、玻璃纤维、芳香族聚酰胺纤维、氧化铝纤维、碳化硅纤维、硼纤维、金属纤维、天然纤维、矿物纤维等。强化纤维可以由上述纤维的任1种构成,也可以由2种以上组合构成。在这些中,从强化纤维的强度、刚性高且质量轻的方面出发,优选PAN系、沥青系、人造丝系等碳纤维。从提高经济性的观点出发,由于强化纤维优选为玻璃纤维,因为更优选包含碳纤维和玻璃纤维。进而,从提高得到的成形品的冲击吸收性等的方面出发,强化纤维优选包含芳香族聚酰胺纤维。另外,从提高得到的成型品的导电性的方面出发,强化纤维也可以是包覆了镍等金属的强化纤维。
强化纤维的形态也没有特别限制。纤维强化树脂例如可以通过使切碎的纤维均匀地分散在基质树脂中而得到,或者也可以通过将基质树脂浸渍在机织物、针织物、无纺布等的对纤维赋予了方向性的纤维片中而得到。
纤维强化树脂即纤维强化复合材料中的基质树脂与强化纤维的比例没有特别限制。举出一例,从强度等机械物性的观点出发,相对于每单位体积的纤维强化复合材料,强化纤维的体积优选为30~70%,更优选为50~60%。另外,相对于每单位体积的纤维强化复合材料,基质树脂的体积优选为30~70%,更优选为40~50%。
本发明的实施方式的纤维强化树脂的制造方法没有特别限制。举出一例,纤维强化树脂可以通过在将双液固化型组合物涂布/含浸于强化纤维后,使双液固化型组合物固化的方法来制作。将双液固化型组合物涂布/含浸的工序能够使用公知的方法(刷、辊等)。另外,使双液固化型组合物固化的工序根据需要可以是在加热环境下(例如60~180℃)进行,也可以是在减压环境下(例如5kPa以下)进行。此时,本发明的实施方式的纤维强化树脂由于可使用上述的双液固化型组合物,因此可改善成形时的作业性。
本实施方式涉及的纤维强化树脂适于作为电子设备壳体,适用于计算机、电视机、照相机、音频播放器等。另外,该纤维强化树脂适于电气电子元件用途,适用于连接器、LED灯、插座、光学拾波器、端子板、印刷基板、扬声器、小型马达、磁头、电源模块、发电机、电动机、变压器、变流器、电压调节器、整流器、逆变器等。进而,复合材料适于汽车部件、车辆关联部件等,适用于安全带部件、仪表板、控制台盒、立柱、上边梁、挡泥板、保险杠、车门板、车顶板、发动机罩板、行李箱盖、车门镜支柱、扰流板、发动机罩散热栅、车轮盖、车轮罩、装饰件、进气歧管、燃料管、引擎冷却水接头、车窗清洗喷嘴、刮水器、电池周边部件、线束连接器、灯罩、灯反射器、灯座等。此外,该纤维强化树脂适于作为建材,适用于土木建筑物的墙壁、屋顶、天花板材料相关部件、窗户材料相关部件、隔热材料相关部件、地板材料相关部件、隔震减振部件相关部件、关键基础设施相关部件等。此外,该纤维强化树脂适于作为运动用品,适用于高尔夫球杆杆身、高尔夫球等高尔夫相关用品、网球拍、羽毛球拍等运动球拍相关用品、美式足球、棒球、垒球等的面具、头盔、护胸、护肘、护膝等运动用身体保护用品、钓鱼竿、线轴、饵等钓具相关用品、滑雪杆、滑雪板等冬季运动相关用品等。
[作用效果]
本发明的实施方式能够提供即使混合时和成形时的树脂粘度低也具有高玻璃化转变温度的热塑性树脂。由于成形时的树脂粘度低,因此能够提高与强化纤维复合化时的基质树脂的流动性,提高成形作业性。
另外,通过将像这样具有高玻璃化转变温度且为热塑性的树脂用作纤维强化复合材料的基质树脂,从而在固化后也能够进行基于热的加工。因此,例如,也能够预先制作平板状的纤维强化复合材料,使用其进行利用热而成形为曲面状的加工,加工性优异。而且,由于像这样能够进行基于热的加工,并且玻璃化转变温度高,从而能够提高实际的使用环境下的耐热性,从而能够提供耐热性高的纤维强化复合材料。因此,能够将用途扩大到接近热源的部件等。
实施例
以下,举出实施例并进一步具体说明本发明,但只要不超出本发明的要旨,则本发明不限于以下的实施例。
按照下述表1、2所示的配合(质量份),制备实施例1~21以及比较例1~4的双液固化型组合物。详细而言,混合除了多异氰酸酯组分以外的成分,制备多元醇组分(第1液),将得到的第1液调整到25℃,在其中添加调整到25℃的多异氰酸酯组分(第2液),搅拌混合1分钟。表1、2中的成分的细节如下所述。
[具有芳香环的二醇(A-1)]
·A-1-1:双酚A的环氧丙烷加成物(分子量:360)
ADEKA公司制“Adeka Polyether BPX-11”
·A-1-2:双酚A的环氧丙烷加成物(分子量:532)
三洋化成公司制“NEWPOL BP-5P”
·A-1-3:双酚A的环氧乙烷加成物(分子量:672)
三洋化成公司制“NEWPOL BPE-100”
·(比较用材料)A-1C:双酚A的环氧丙烷加成物(分子量:790)
ADEKA公司制“Adeka Polyether BPX-55”
[不具有芳香环的二醇(A-2)]
·A-2-1:1,4-丁二醇(分子量:90)
三菱化学公司制“1,4-丁二醇”
·A-2-2:二丙二醇(分子量:134)
旭硝子公司制“二丙二醇”
·A-2-3:2-乙基-1,3-己二醇(分子量:146)
KH Neochem Co.,Ltd.制“2-乙基-1,3-己二醇”
·A-2-4:三丙二醇(分子量:192)
旭硝子公司制“三丙二醇”
·A-2-5:聚丙二醇(分子量400)
旭硝子公司制“Exenol 420”
·(比较用材料)A-2C:聚丙二醇(分子量1000)
旭硝子公司制“Exenol 1020”
[芳香族二异氰酸酯(B-1)]
·B-1-1:MDI(4,4'-MDI与2,4'-MDI的混合物(50%:50%))
BASF INOAC Polyurethanes Ltd.制“Lupranate MI”
·B-1-2:MDI(4,4'-MDI)
TOSOH CORPORATION制“MILLIONATE MT”
·B-1-3:碳二亚胺改性MDI(4,4'-MDI的碳二亚胺改性体与4,4'-MDI的混合物(25%:75%))
BASF INOAC Polyurethanes Ltd.制“Lupranate MM-103”
[多孔质粉体(C)]
·C-1:沸石
Union Showa公司制“Molecular sieve 3AB”
[其他(D)]
·D-1:二月桂酸二辛基锡(金属催化剂)
日东化成产业株式会社制“Neostan U810”
[评价]
对于实施例1~21和比较例1~4的双液固化型组合物,根据以下的评价方法,评价混合粘度、玻璃化转变温度(Tg)、拉伸强度、热熔融温度、纤维强化树脂的弯曲强度以及纤维强化树脂的冲击强度。在表1和表2中示出结果。
(1)混合粘度(mPa·s)
将各上述混合物静置在25℃环境下,测定从混合开始起5分钟后的粘度。粘度按照JIS K7117-1使用BM型粘度计(东机产业株式会社制)进行测定。
(2)玻璃化转变温度(℃)
以混合后经过5分钟时膜厚为1mm的方式涂布各上述混合物。通过将其在120℃处理1小时,由此得到聚氨酯树脂的片材。从得到的树脂片切出5mm×2cm的试验片,按照JISK7244-4,用UBM公司制的Rheogel E-4000测定玻璃化转变温度。
(3)拉伸强度(MPa)
通过与玻璃化转变温度同样的方法,得到膜厚1mm的聚氨酯树脂的片材。从得到的片材切出5mm×4cm的试验片,按照JIS A6021-2011,使用Instron Japan公司制的数字万能试验机(Instron 5581)测定拉伸强度(MPa)。
(4)热熔融温度
通过与玻璃化转变温度同样的方法,得到膜厚1mm的聚氨酯树脂的片材。从得到的片材切出1mm×1mm的试验片,按照JIS K7210,用岛津制作所公司制的流动性试验机(岛津Flow tester CFT-500D)测定1/2法温度。
(5)纤维强化树脂(CFRP)的弯曲强度
将平织的碳纤维重叠在产品模具上,将其用脱模膜覆盖并封闭而形成真空封装后,注入树脂,在120℃下进行1小时固化,得到膜厚2mm的纤维强化树脂成型体。从得到的成型体切出100mm×15mm×2mm的试验片,按照JIS K7074,使用精密万能试验机(岛津AUTOGRAPH AG-X plus)测定3点弯曲强度。
(6)纤维强化树脂的夏比冲击试验(冲击强度)
通过与弯曲强度同样的方法,得到膜厚2mm的纤维强化树脂成型体。从得到的成型体切出80mm×10mm×2mm的试验片,按照JIS K7077,用摆锤冲击试验机(Instron MPX系列电动摆式试验机)测定夏比冲击强度。
[表1]
[表2]
当为实施例1~21的双液固化型组合物时,混合粘度低,并且得到的热塑性树脂的玻璃化转变温度高。可知,特别是在具有芳香环的二醇(A-1)的分子量为200~500且不具有芳香环的二醇(A-2)的分子量为120以下的情况下,能够实现更高的玻璃化转变温度。另外,得到的热塑性聚氨酯树脂具有某种程度的拉伸强度。
另外可知,在使用实施例1~21的双液固化型组合物的固化物作为纤维强化树脂的基质树脂的情况下,该纤维强化树脂具有某种程度的弯曲强度、冲击强度。由此也可以说,本发明的实施方式涉及的双液固化型组合物适于作为纤维强化树脂制造用。
另一方面,在比较例1~比较例4中,无法同时实现既抑制混合粘度又提高玻璃化转变温度。另外,在比较例3和4中,由于混合粘度过高,导致无法含浸于强化纤维,因此无法对其弯曲强度和冲击强度进行评价。
以上,说明了本发明的若干实施方式,但这些实施方式仅作为示例而给出,并非意图限定发明的范围。这些实施方式能够以其他各种方式实施,在不脱离发明的主旨的范围内能够进行各种省略、替换和变更。这些实施方式或其省略、替换、变更等不仅包含在发明的范围、主旨中,同样也包含在权利要求书所记载的发明以及与其均等的范围中。
Claims (8)
1.一种热塑性聚氨酯树脂制造用双液固化型组合物,其具有包含二醇(A)的多元醇组分以及包含二异氰酸酯(B)的多异氰酸酯组分,其中,
所述二醇(A)包含分子量为200~700的具有芳香环的二醇(A-1)和分子量为500以下的不具有芳香环的二醇(A-2),
所述二醇(A-1)相对于所述二醇(A-1)与所述二醇(A-2)的合计的质量比((A-1)/((A-1)+(A-2)))为(10/100)~(75/100)。
2.根据权利要求1所述的热塑性聚氨酯树脂制造用双液固化型组合物,其中,
所述不具有芳香环的二醇(A-2)是脂肪族二醇和具有氧亚烷基的二醇中的至少任一者。
3.根据权利要求1或2所述的热塑性聚氨酯树脂制造用双液固化型组合物,其中,
所述二异氰酸酯(B)包含芳香族二异氰酸酯(B-1)。
4.根据权利要求1~3中任一项所述的热塑性聚氨酯树脂制造用双液固化型组合物,其中,
所述具有芳香环的二醇(A-1)是双酚A的环氧烷加成物。
5.根据权利要求1~4中任一项所述的热塑性聚氨酯树脂制造用双液固化型组合物,其中,
所述多元醇组分还包含多孔质粉体(C)。
6.根据权利要求1~5中任一项所述的热塑性聚氨酯树脂制造用双液固化型组合物,其中,
所述热塑性聚氨酯树脂制造用双液固化型组合物用于纤维强化树脂的制造。
7.一种热塑性聚氨酯树脂,其中,
所述热塑性聚氨酯树脂包含权利要求1~6中任一项所述的热塑性聚氨酯树脂制造用双液固化型组合物的反应物。
8.一种纤维强化树脂,其中,
所述纤维强化树脂包含权利要求7所述的热塑性聚氨酯树脂和强化纤维。
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